Selenium Adsorption Research Articles

Enhancing Selenium Removal Using Pre-Treated Natural Clay: Experimental Investigation and Predictive Modeling

Abstract A heat treatment methodology was adopted as a pretreatment strategy, altering the porous structure of the clay to minimize leaching for selenium adsorption in an aqueous system. Rigorous experiments were carried out in batch mode to determine optimal parameters across various variables, including contact time, adsorbent dosages, selenium concentrations, pH, temperature, and stirring speed during selenium removal using natural clay. Investigating several kinetic and isotherm models revealed the best fitting for the pseudo-second-order and the Langmuir isotherm. Endothermic and spontaneous characteristics of the adsorption process were shown during thermodynamic analysis. In this study, a predictive model for the efficiency of selenium separation was established using Response Surface Methodology (RSM). Additionally, an Artificial Neural Network (ANN), a data-driven model, was employed for comparative analysis. The predictive model exhibited a high degree of agreement with experimental data, demonstrated by a low relative error of <0.10, a high regression coefficient of >0.97), and a substantial Willmott-d index of >0.95. Moreover, the efficacy of pre-activated clay in selenium removal was assessed, revealing the superior performance of ANN models over RSM models in forecasting the efficiency of the adsorption process. This research significantly advances an effective and sustainable material for selenium removal, providing valuable insights into predictive modeling techniques applicable to similar contexts to boost scale-up confidence during industrial implementation in affected regions.

Passivation of Deep‐Level Defects through Chemical Environment Regulation for Efficient CZTSSe Solar Cells Based on Active Selenium Adsorption–Desorption Process

AbstractInsufficient selenization and uneven distribution of elements caused by the poor diffusion and reaction activity of selenium clusters is one of the main issues limiting the efficiency of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Here, this work designs a simple and feasible strategy to improve the activity of selenium (Se) by implementing high‐temperature treatment on graphite boxes loaded with Se pellets. The rapid adsorption/desorption characteristics of graphite on active gaseous small‐molecule selenium have successfully introduced hyperactive Se4, Se3, and Se2 into the selenization process. The results indicate that the adsorbed non‐toxic gaseous active Se3 and Se4 can quickly and uniformly diffuse into the precursor film at low temperatures, thereby inducing nucleation and grain growth at both surface and back interface simultaneously, which inhibits the upward migration and aggregation of cations, especially Cu, and promotes the homogenization of elements. The overall relatively Cu‐poor chemical environment suppresses the formation of CuZn defects and [2CuZn+SnZn] defect clusters, and also promotes the generation of favorable VCu. The band tail states and non‐radiative recombination are then optimized. Finally, the CZTSSe solar cells achieve a power conversion efficiency (PCE) of 14.5%, with VOC/VOCSQ of 67% being one of the highest in the literature.

Selenium Adsorption on the (111), (100), (110) and (211) Surfaces of Face‐Centered‐Cubic Metals: Density Functional Calculations of the Potential Energy Surfaces

AbstractIn this study, we expand the computational investigation of selenium, which has previously been limited to metals such as Cu, Fe, Pd, Au, and Pt. Utilizing density functional theory calculations, we explore the adsorption and diffusion of selenium at a low‐coverage regime of 0.25 ML on a broader range of metal surfaces, including Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au. Our results reveal that selenium exhibits a distinct preference for three‐fold or four‐fold high‐coordination sites on most studied surfaces. We further analyze the minimum energy diffusion pathways, demonstrating that the energy barrier for selenium's surface diffusion varies significantly based on the orientation and nature of the metal surfaces. Specifically, on (100) surfaces, selenium exhibits the highest diffusion energy, ranging from 0.60 eV in Au(100) to 1.12 eV in Pd(100). The diffusion behavior on (110) and (211) surfaces is also elaborated, emphasizing the unique trends observed compared to previously studied elements like sulfur. Importantly, this study is a new reference for future computational analyses, filling existing gaps by providing comprehensive data on selenium adsorption on various face‐centered cubic metal surfaces not previously reported.

Layered Double Hydroxides as Next-Generation Adsorbents for the Removal of Selenium from Water

This research paper provides a comprehensive overview of the use of layered double hydroxides (LDH) in the removal of selenium species from contaminated water sources. Key studies on sorption mechanisms and the impact of competing ions on selenium removal are presented, and the effectiveness of LDH is compared across different structures and compositions. Scholarly sources extensively document the application of conventional LDH for effective selenium removal, with notable advancements achieved through innovative synthesis approaches. Comparative studies between LDH synthesized through various methods reveal the potential of tailored LDH for enhanced selenium adsorption. The paper further explores the influence of competing anions on LDH efficacy, emphasizing the impact of sulfate on selenium removal. Additionally, investigations into calcined LDH and commercially available variants underscore the potential for industrial applications. Beyond conventional LDH, the paper delves into iron-based LDH, LDH with intercalated thiomolybdate anions, and layered rare earth hydroxides, exploring their effectiveness in separating different selenium species. The role of pH in the removal of selenium species and the impact of three-metal cation LDH are also discussed. The study extends to nanocomposites, combining LDH with zero-valent iron, carbon-based materials, and organic compounds, illustrating their potential for selenium species immobilization. The presented findings offer valuable insights for researchers and practitioners in environmental science, addressing the growing demand for efficient selenium remediation strategies.

Amino-functionalization of PVA/TiO2-CeO2 nanohybrid adsorbent for the removal of selenium ions from aqueous solutions: Equilibrium and kinetics studies

ABSTRACT In this study, a hybrid nanoadsorbent (HnA), (PVA/TiO2-CeO2), was synthesized and amino-functionalized by 3-aminopropyltriethoxysilane (APTES) to produce AHnA, for use in an advanced selenium adsorption study focusing on nonlinear equilibrium and kinetics models. AHnA was characterized using XRD, FTIR spectroscopy, SEM, and EDX elemental analyses, as well as BET-BJH techniques. According to the FTIR results, APTES has successfully cross-linked the PVA chain and introduced amine groups on the surface. Moreover, the modification resulted in an increase in the total pore volume from 0.0061 cm3/g in HnA to 0.021 cm3/g in AHnA. Several adsorption experiments were conducted to determine the impact of varying contact times within a pH range of 1 to 8 and concentrations ranging from 5 to 200 mg/L, using a One-Variable-At-a-Time (OVAT) procedure. Accordingly, a dosage of 2 g/L of modified nanocomposite exhibits optimal performance for removing selenium from a 20 mg/L solution at an acidic pH of 3 during 300 minutes of contact with selenium ions, while conforming to a pseudo-second-order kinetic model. The assessment of various nonlinear isotherm models for analyzing equilibrium data revealed that the experimental data of selenium adsorption conformed to a generalized isotherm, showing a maximum monolayer adsorption capacity of 17.643 mg/g.

Adsorption of Chromium, Copper, Lead, Selenium, and Zinc ions into ecofriendly synthesized magnetic iron nanoparticles.

The iron nanoparticles (Fe-NPs) have been synthesized using an environmentally friendly and simple green synthesis method. This study aims to obtain an aqueous extract from natural material wastes for synthesizing Fe-NPs. The produced Fe-NPs were evaluated as adsorbents for removing Pb, Se, Cu, Zn, and Cr from aqueous solutions. The formation of Fe-NPs was observed on exposure of the aqueous extract to the ferrous chloride and ferric chloride solutions. The characterization of the synthesized Fe-NPs was carried out using different instrumental techniques. As a function of the initial metal ion concentration, contact time, and various doses, the removal of the heavy metal ions was investigated. The UV-Vis spectrum of Fe-NPs showed a peak at 386 nm, 386 nm, 400 nm, 420 nm, 210 nm, 215 nm, and 272 nm of banana, pomegranate, opuntia, orange, potato, and onion, respectively. The FT-IR spectra confirmed the attachment of bioactive molecules from plants on the Fe-NPs surface. The effective reduction of metal ions was greatly aided by the -OH functional groups. The functional groups were examined and responsible for adsorption process by nanoparticle powder sample, these peaks are 3400 cm-1, 2900 cm-1, 1600 cm-1,1000 cm-1, and 1550 cm-1. The magnetization measurements revealed superparamagnetic behavior in the produced iron oxide nanoparticles. Heavy metal ions uptake followed a time, dose, and initial concentration-dependent profile, with maximum removal efficiency at 45 min, 0.4 g, and 3.0 mg/L of metal concentration, respectively.

Efficient adsorption of selenium (Se(IV) and Se(VI)) from water using Acacia senegal polysaccharide with multiple amine groups: Synthesis and application

In this study, an amine-rich gel (ARAS) was prepared by chemically altering Acacia senegal (AS). ARAS acts as an adsorbent for selenium. Owing to the introduction of amino functional groups and a remarkable specific surface area (91.89 g/m2), ARAS shows maximum adsorption capacities at 75 and 130 mg g−1 for Se(IV) and Se(VI), respectively. The removal efficiency of ARAS is higher (ωSeIV = 98.2 % and ωSeVI = 98.6 %) at lower concentrations (CSeIV = 100 ppm and CSeVI = 95 ppm) and the adsorption equilibrium is achieved within 60 min. The adsorption process of Se (IV) and Se (VI) via ARAS is elucidated using the Quasi-Second-Order kinetic and Langmuir models. The enhanced adsorption capacity of the adsorbent could be attributed to the synergistic effects of electrostatic attraction, hydrogen bonding, and specific physicochemical properties. Thermodynamic studies reveal that the surface adsorption process is spontaneous and exothermic. Notably, ARAS maintains remarkable adsorption stability under a variety of solution conditions, including variable pH (4–11), NaCl concentrations (0–1 M), and the presence of organic solvents. It retains approximately 60 % of its initial adsorption capacity for Se(IV) and Se(VI) after three adsorption cycles. Therefore, ARAS with its cost-effectiveness and exceptional performance shows considerable potential for applications in water treatment.

Selenite Adsorption and Reduction via Iron(II) Impregnated Activated Carbon Produced from the Phosphoric Acid Activation of Construction Waste Wood.

Chemical activation of waste materials, to form activated carbon, (AC) is complicated by the large amounts of chemical activating agents required and wastewater produced. To address these problems, we have developed an optimized process for producing AC, by phosphoric acid activation of construction waste. Waste wood from construction sites was ground and treated with an optimized phosphoric acid digestion and activation that resulted in high surface areas (> 2000 m2/g) and a greater recovery of phosphoric acid. Subsequently the phosphoric acid activated carbon (PAC), was functionalized with iron salts and evaluated for its efficacy on the adsorption of selenite and selenate. Total phosphoric acid recovery was 96.7% for waste wood activated with 25% phosphoric acid at a 1:1 ratio, which is a substantially higher phosphoric acid recovery, than previous literature findings. Post activation impregnation of iron salts resulted in iron(II) species adsorbed to the PAC surface. The iron(II) chloride impregnated AC removed up to 11.41 ± 0.502mg selenium per g Iron-PAC. Competitive ions such as sulfate and nitrate had little effect on selenium adsorption, however, phosphate concentration did negatively impact the selenium uptake at high phosphate levels. At 250ppm, approximately 75% of adsorption capacity of both the selenate and the selenite solutions was lost, although selenium was still preferentially adsorbed. Peak adsorption occurred between a pH of 4 and 11, with a complete loss of adsorption at a pH of 13.

Ultrasensitive determination of selenium in water and food samples by ICP-MS: UiO-66-NH2 for preconcentration and direct slurry hydride generation

BackgroundSelenium is an indispensable microelement for humans and food is the main source of selenium intake. As one of the best techniques for the determination of selenium, inductive coupling plasma-mass spectrometry (ICP-MS) features some unique advantages, such as wide linear range and high sensitivity. Nevertheless, it still remains a challenge to achieve the accurate and high sensitivity determination of ultra-trace selenium in food samples by ICP-MS owning to the high first ionization energy of selenium and interferences from sample matrices as well as isobaric interferences. ResultsIn this work, UiO-66-NH2 (metal organic framework, MOF) was fast synthesized by microwave method and employed for the preconcentration of ultra-trace selenium with an adsorption efficiency of nearly 100%. The selenium-adsorbed MOF was collected by filtration, and then simply converted to slurry for in situ hydride generation (HG) for sensitive detection of selenium by ICP-MS. Various factors affecting the adsorption of selenium by the MOF (including pH, adsorption time, and amount of MOF) together with main parameters of hydride generation (including concentrations of HCl and NaBH4) were carefully evaluated. Experimental results show that effective matrix separation can greatly reduce interference, with an excellent detection limit of 1 ng/L. The practicability and accuracy of this method were successfully confirmed by the determination of trace selenium in several food samples. SignificanceUiO-66-NH2 (MOF) was used as an effective adsorbent for the preconcentration of selenium prior to direct slurry sampling HG-ICP-MS determination. Direct slurry sampling avoided additional elution procedures and was conducive to eliminating matrix and isobaric interferences. High sensitivity and anti-interference determination were achieved for determination of ultra-trace Se in complex food samples.

Phosphorus can effectively reduce selenium adsorption in selenium-rich lateritic red soil

Phosphorus (P) application can improve the availability of selenium (Se) in soil, which benefits the output of Se-rich agricultural products. However, the mechanism by which P affects the adsorption of Se in Se-rich soil is still unclear. Therefore, this study took Se-rich lateritic red soil as the research object and studied the adsorption behavior of P and Se in the soil through batch adsorption tests and soil characterization technology. The results showed that the adsorption of P or Se in lateritic red soil increased with an increase in equilibrium concentration. The P or Se adsorption process was explained using the Langmuir and Freundlich isotherm models. After adding P, the adsorption of Se decreased from 276–423 mg/kg to 52–201 mg/kg at different initial Se concentrations. The scanning electron microscope and energy dispersive spectrometry (SEM-EDS) results showed that the lateritic red soil was rich in C, O, Fe, Al, and other elements, and the free oxidation states of these elements could efficiently facilitate the adsorption of P and Se. Fourier infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analyses indicated that both Se and P could react with ferrite groups in the soil to form iron-containing complexes, and there was a competitive adsorption phenomenon, which was the main reason for the decrease in Se adsorption. This study provides theoretical support for further exploring the effect of P on Se behavior in the geochemical cycle. Furthermore, it promotes the efficient use of Se-rich soil resources.

The potential of a natural Ecuadorian mordenite-type zeolite for batch and column selenium removal

ABSTRACT Selenium is found in natural waters of developing countries. The present study refers to Se (IV) adsorption onto an Ecuadorian natural zeolite, activated at 225°C. Its physicochemical characterization included particle size analysis, XRD, SEM-EDX, and FTIR. After selenium adsorption, the FTIR spectra denoted the presence of moved bands and new peaks, probably corresponding to new metal bond vibrations. Batch experiments were carried out at 26°C, for 2 h, at adsorbate doses within 0.01–50 mg L−1, bringing about a removal percentage in the range of 57−90%. Eventually, Se (IV) adsorption was performed at a pH of 7.5, resembling realistic well-water matrix conditions. Zeolite accomplished a maximum Se adsorption capacity of 53 mg g−1 zeolite, corresponding to roughly 90% of Se removal. The results obtained upon constant flow mode were analyzed with various kinetic models, appearing Thomas and BDST models to fit better. The highest Se removal percentage on typical well waters leaves a Se value lower than the permissible levels. Thus, natural zeolites offer an economic and competitive alternative for Se (IV) removal, especially from groundwater and industrial wastewater in developing countries.

Selenite Removal from Aqueous Solution Using Silica-Iron Oxide Nanocomposite Adsorbents.

In recent years, during industrial development, the expanding discharge of harmful metallic ions from different industrial wastes (such as arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, or zinc) into different water bodies has caused serious concern, with one of the problematic elements being represented by selenium (Se) ions. Selenium represents an essential microelement for human life and plays a vital role in human metabolism. In the human body, this element acts as a powerful antioxidant, being able to reduce the risk of the development of some cancers. Selenium is distributed in the environment in the form of selenate (SeO42-) and selenite (SeO32-), which are the result of natural/anthropogenic activities. Experimental data proved that both forms present some toxicity. In this context, in the last decade, only several studies regarding selenium's removal from aqueous solutions have been conducted. Therefore, in the present study, we aim to use the sol-gel synthesis method to prepare a nanocomposite adsorbent material starting from sodium fluoride, silica, and iron oxide matrices (SiO2/Fe(acac)3/NaF), and to further test it for selenite adsorption. After preparation, the adsorbent material was characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism associated with the selenium adsorption process has been established based on kinetic, thermodynamic, and equilibrium studies. Pseudo second order is the kinetic model that best describes the obtained experimental data. Also, from the intraparticle diffusion study, it was observed that with increasing temperature the value of the diffusion constant, Kdiff, also increases. Sips isotherm was found to best describe the experimental data obtained, the maximum adsorption capacity being ~6.00 mg Se(IV) per g of adsorbent material. From a thermodynamic point of view, parameters such as ΔG0, ΔH0, and ΔS0 were evaluated, proving that the process studied is a physical one.

Improvement of selenium adsorption performance at high temperature by CaO/ZSM-5 composite sorbents

ABSTRACT Selenium in flue gas from coal combustion, released into the atmosphere, will affect the environment and human health greatly. The adsorption method can achieve good control of selenium emission, by using CaO as adsorbent, but CaO is easy to sinter at high temperature, resulting in the decrease of adsorption capacity. Therefore, thermostability ZSM-5 molecular sieve was added to prepare composite adsorbent to improve the adsorption performance for selenium at high temperature. CaO/ZSM-5 composite adsorbent was prepared by impregnation method, and its adsorption performance and mechanism were studied. The results show that the composite adsorbent shows stronger adsorption capacity at high temperatures. The mixing ratio has a great influence on the microstructure of the composite adsorbent influencing the adsorption capacity. When the ratio is 1:1, the adsorption efficiency of the composite adsorbent shows a good performance. At 900°C, the adsorption efficiency of Z1C1(ZSM-5/CaO = 1:1 wt%) can still maintain 67%, which is 32% higher than that of CaO. Si and Al in the composite adsorbent have different effects on the improvement of microstructure. The existence of Si is conducive to maintaining the stable skeleton of the composite adsorbent, improving anti-sintering, while the addition of Al tends to improve the porosity, furtherly ameliorating the structure of the composite adsorbent for high-temperature adsorption.

Insight into the role of SO2 on selenium conversion during adsorption by CaO: Theoretical calculation and experimental study

SO2 can noticeably impact the control of high toxic selenium emissions from flue gas by CaO. Surprisingly, our experiments showed that under certain conditions, SO2 can promote selenium capture by CaO, rather than hinder it. To elucidate the underlying mechanism, a combination of theoretical calculations and experiments was conducted. Thermodynamic equilibrium analysis revealed that gaseous SO2 and solid Ca-S reaction products can promote SeO2 converting to SeO/Se0. The Ca-S products facilitated greater SeO2 conversion compared to SO2. Experimental results demonstrated that selenium adsorption capacity of incompletely sulfurized CaO (CaO with pre-adsorbed SO2) was higher than that of completely sulfurized CaO (Ca-S products), highlighting the importance of adsorption sites of CaO. Density functional theory calculations showed that the pre-adsorbed SO2 hardly affected selenium adsorption energy on the SO2/CaO surface, while completely sulfurized CaO had low selenium adsorption energy, explaining the experimental phenomenon and proving necessary of CaO. Additionally, SeO/Se0 had higher adsorption energy on CaO than SeO2. Overall, the promotion of SO2 on selenium adsorption was primarily affected by two factors: 1) sulfur facilitating SeO2 conversion to SeO/Se0 which can be adsorbed more easily by CaO; 2) sufficient adsorption sites on CaO surface existing for SeO/Se0 adsorption, despite co-adsorption with sulfur.

The interference of marine accidental and persistent petroleum hydrocarbons pollution on primary biomass and trace elements sink

More than 80 % of the primary biomass in marine environments is provided by phytoplankton. The primary mechanism in the trace element sink is the absorption of trace elements by phytoplankton. Because of their difficult degradability and bioaccumulation, petroleum hydrocarbons are one of the most significant and priority organic contaminants in the marine environment. This study chose Chlorella pyrenoidosa as the model alga to be exposed to short and medium-term petroleum hydrocarbons. The ecological risk of accidental and persistent petroleum hydrocarbon contamination was thoroughly assessed. The interaction and intergenerational transmission of phytoplankton physiological markers and trace element absorption were explored to reflect the change in primary biomass and trace element sink. C. pyrenoidosa could produce a large number of reactive oxygen species stimulated by the concentration and exposure time of pollutants, which activated their antioxidant activity (superoxide dismutase (SOD) activity, β-carotene synthesis, antioxidant trace elements uptake) and peroxides production (hydroxyl radicals and malondialdehyde). The influence of the growth phase on SOD activity, copper absorption, and manganese adsorption in both persistent and accidental pollution was significant (p < 0.05, F > Fα). Adsorption of manganese and selenium positively connected with SOD, malondialdehyde, and Chlorophyl-a (p < 0.01). These findings convincingly indicate that petroleum hydrocarbon contamination can interfere with primary biomass and trace element sinks.

Evaluation of Agrowaste Species for Removal of Heavy Metals from Synthetic Wastewater

This study’s goal was to learn more about how agrowaste plants tolerate, absorb, and accumulate a number of metals that are of relevance to the environment. Adsorption of lead (Pb), chromium (Cr), selenium (Se), copper (Cu), and zinc (Zn) ions from synthetic aqueous solutions and wastewater using natural waste residues (NWRs) such as moringa, Lupinus, sugarcane straw, and tea residue was evaluated. The adsorbents used for this study were prepared by washing, drying, and grinding. Fourier-transform infrared (FT-IR) spectroscopy and scanning electron microscope (SEM) analysis were used to characterize the adsorbents’ waste residues. The effect of different parameters such as pH, dose of adsorbents, and the initial concentration of heavy metals, as well as the adsorption isotherm parameters were studied. Moringa, Lupinus, sugarcane straw, or tea residue results were found to fit the Langmuir and Freundlich adsorption isotherms. The adsorption capacity reached 14.59, 16.10, 12.73, and 15.01 mg/g, respectively. The adsorption study’s overall results indicated the removal efficiency pattern as moringa &gt; tea &gt; Lupinus &gt; sugarcane straw. At a dose of 0.5 g/L, the maximum removal percentages for lead, chromium, selenium, copper, and zinc ions were 90.2, 76.55, 70.55, 76.6, and 78.9, respectively. The materials might be regarded as efficient adsorbents for extracting the ions Pb, Cr, Se, Cu, and Zn from wastewater, according to the research.

Oxygen-vacancy enhanced CoO/CeO2 heterojunction for synchronous regulation of sulfur resourcing and selenium adsorption separation from flue gas desulfurization wastewater

A dual functional material of oxygen-vacancy-enriched cobalt-ceria bimetallic oxide (OV-CoO/CeO2) provides a new method for the simultaneous production of high-quality sulfate and separation of toxic Se from flue gas desulfurization wastewater.

Migration and emissions of selenium during chemical looping combustion of coal

AbstractSelenium is one of the most volatile toxic elements in coal, and its emissions must be strictly controlled. Chemical looping combustion (CLC) is a clean and efficient technology for coal. Herein, the iron‐based oxygen carrier (OC) was used as an adsorbent to study the migration and emissions of selenium during the CLC of coal. Due to the oxidation and adsorption of selenium by iron‐based OC, most of the selenium was retained in OC or distributed in the CO2 stream. The proportion of gaseous selenium released into the atmosphere was less than 10%—significantly lower than that from the traditional combustion process of coal, which had a value of 91.79%. The presence of OC increased the distribution phase of selenium, promoted the conversion of gaseous selenium to solid selenium, and reduced selenium emissions in flue gas. During CLC of coal, the fuel reactor (FR) temperature and the number of OC re‐oxidation cycles played an important role in the emissions and retention of selenium. The increasing FR temperature increased the gaseous selenium in the CO2 stream, reduced the particulate selenium absorbed by OC, and reduced the selenium emissions in the atmosphere. After 10 continuous CLC cycles, the selenium concentration in OC increased from 0.889 to 8.20 mg kg−1. The continuous cycling of CLC could realize the enrichment of selenium from coal to OC. Furthermore, the migration and transformation mechanism of selenium during CLC was deduced by experiments and thermodynamic simulation. This research provides a suitable reference for reducing selenium emissions and developing CLC technology.

Cloning the Dirac cones of bilayer graphene to the zone center by selenium adsorption

Dirac cones can foster extraordinary electronic effects, as exemplified by the case of graphene layers. Angle-resolved photoemission reveals that adsorption of selenium (Se) vapor on bilayer graphene creates a symmetric hybrid clone of the Dirac cones at the zone center. A detailed analysis aided by first-principles calculations shows that the adsorbed layer consists of an ordered array of Se8 molecules. The uncovered cloning mechanism illustrates a method to generate electronic features of scientific and technological interests by gentle surface modification via van der Waals adsorption.

Partitioning and transformation behavior of selenium during coal combustion

The partitioning of selenium in coal-fired flue gas and desulfurization wastewater is of great threat to the ecological environment and human health. However, the unclear understanding of interactions between selenium vapors and fly ash hinders the emission control of selenium from coal-fired power plants. To further illuminate the mechanism of selenium partitioning and transformation, this study carefully estimated selenium distribution characteristics in the coal combustion byproducts from several industrial power plants. The effective temperature range as well as the key ash components for selenium retention by fly ash was clarified by multiple-scale experiments and theoretical perspectives. The results showed that gaseous selenium tended to be captured by fly ash at a medium-to-low temperature range (i.e. below 650 °C). The limited residence time resulted in the incomplete capture of gaseous selenium by fly ash. Mullite, quartz, iron oxides, and anhydrite in fly ash were found to be the main trappers for gaseous selenium. Among these components, iron oxides showed excellent selenium adsorption performance at a wide temperature range of 150-700 °C, which was realized by the strong chemical adsorption. By contrast, as the dominant phases in fly ash for the physical adsorption of gaseous selenium, mullite and quartz mainly captured gaseous selenium below 300 °C. On the other hand, sulfur dioxides had priority over gaseous selenium to react with calcium-containing ash components by forming anhydrite in the high-temperature region. The formed anhydrite had a limited selenium adsorption capacity, which was confirmed to capture gaseous selenium through a combination of physical adsorption and weak chemical adsorption. For the in-depth control of selenium emitted into desulfurization system and atmosphere environment, these findings provided a comprehensive insight into the behavior of selenium partitioning and transformation into fly ash during coal combustion.